Stabilized vegetable oils and methods of making same

ABSTRACT

A method for modifying ethylenic unsaturation in a triglyceride. One or more unsaturated fatty acyl moieties present in the triglyceride are substituted with a lactone or ketone moiety via an electron acceptor mediated reaction. The resulting reaction products are useful, for example, as formulations for lubricants, hydraulic fluids, dielectric fluids, and intermediates for polymer synthesis.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. Ser. No. 11/839,853, filed Aug. 16, 2007, which claims the benefit of U.S. Provisional Application No. 60/822,617, filed Aug. 16, 2006. Each of the applications cited above is incorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION

The present invention relates to unsaturated fatty acyl moieties of free fatty acids, glycerides and other esters, in which sites of ethylenic unsaturation are stabilized via conversion to other moieties, including lactone, ketone, and vinyl groups. Compounds that are, or include, partial or complete lactone, ketone, or vinyl analogs of fatty acyl moieties are also contemplated, in which lactone, ketone, or vinyl moieties are linked into a hydrocarbon chain.

Vegetable oils have some characteristics that favor their use as, or as a component in, lubricant formulations, hydraulic fluid formulations, and dielectric fluid formulations, including dielectric cooling fluid formulations. The long chain fatty acid and ester functionality of vegetable oils gives them good characteristics with respect to lubricity. They also have good resistance to passing electrical currents. Their biodegradability and status as a renewable feedstock also give them advantages over petroleum-based products.

Vegetable oils, however, have shortcomings that have limited their use in lubricants, hydraulic fluids, and dielectric fluids, including dielectric cooling fluids. Vegetable oils have relatively low oxidative stability and relatively high pour points. Vegetable oils also tend to solidify when held at their pour points, unlike petroleum-based products. The oxidative stability problem is due to sites of ethylenic unsaturation (i.e. C.dbd.C bonds) in the hydrocarbon chains of fatty acyl moieties (i.e. R—C(O)—, where R is an ethylenically unsaturated hydrocarbon moiety) of vegetable oils, with fatty acyl moieties containing more than one ethylenic double bond being particularly prone to oxidation.

These shortcomings have been addressed in many ways, such as additive packages containing antioxidants and pour point depressants and the use of synthetic esters, poly alpha olefins or other compounds as diluents to improve pour point.

The oxidative stability problem has been more directly addressed by partial hydrogenation to reduce the number of ethylenic double bonds, partial polymerization (heat bodying), breeding or artificial genetic modification of the oil-producing plants to increase the level of monounsaturated fatty acids in the oil, or hydroxylation followed by esterification of short chain fatty acids to the free hydroxyl groups (U.S. Pat. No. 6,583,302 B1 Erhan et al). Esters have been made with fatty acids and on the fatty acid chains of hydroxylated fatty acids (U.S. Pat. No. 6,316,649 B1 Cennack et al). In addition some work has been done with the formation of secondary ethers (U.S. Pat. No. 6,201,144 B1 Isbell et al). Free radical chemistry has been used to graft antioxidants into rubber (U.S. Pat. No. 4,739,014 Parks et al).

U.S. Pat. No. 4,011,239 (Heiba, et al) discloses selective reactions of free radicals with olefins in the presence of an ion of Mn, V, or Ce.

U.S. Pat. No. 6,201,143 B1 teaches making a polymer using meadowfoam oil fatty acids or meadowfoam as a starting material to form monomers with fatty acids with vinyl groups and making a polymer out of them. That patent mentions that the resulting polymer has enhanced oxidative stability.

Other documents possibly of interest include U.S. Pat. Nos. 4,014,910 (de Klein); 4,119,646 (Heiba, et al.); 4,175,089 (Heiba, et al.); 4,328,363 (Heiba, et al.); 4,736,063 (Coleman, et al.); 4,380,650 (Coleman, et al.); 4,158,741 (Goi, et al.); 6,201,143 B1; Anatoli Onopchenko and Johannn G. D. Schulz, Oxidation by Metal Salts, J. ORG. CHEM., Vol. 57, No. 16, 1972 pg 2564-2566; Harold E. De La Mare, Jay K. Kochi and Frederick F. Rust, Oxidation and Reduction of Free Radicals by Metal Salts, J. AMER. CHEM. SOC., May 20, 1963, Pg. 1437-1449; E. I. Heiba and R. M. Dessau, Oxidation by Metal Salts. VIII. The Decomposition Of Ceric Carboxylates In The Presence Of Olefins And Aromatic Hydrocarbons, J. AMER. CHEM. SOC., 93:4 Feb. 24, 1971 p. 995-999; E. I. Heiba, R. M. Dessau and P. G. Rodewald, Oxidation by Metal Salts. X. One-Step Synthesis Of (Gamma) Lactones From Olefins, J. AMER. CHEM. SOC., 96:26 Dec. 25, 1974 pg 7977-7981; Barry B. Snider, Manganese(II)-Based Oxidative Free Radical Cyclizations, CHEM. REV. 1996, 96, 339-363; I. E. Heiba, R. M. Dessau, A. L. Williams; P. G. Rodewald, Substituted Gamma Butyrolactones From Carboxylic Acids And Olefins: Gamma-(noctyl)_(—) gamma.sub _(—) butyrolactone, ORGANIC SYNTHESES, COLL. Vol. 7, p 400 (1990) Vol. 61, p. 22 (1983) and Ursula Biermann et al., New Syntheses with Oils and Fats as Renewable Raw Materials for the Chemical Industry, in BIOREFINERIES−INDUSTRIAL PROCESSES AND PRODUCTS: STATUS QUO AND FUTURE DIRECTIONS, Vol. 2 (Birgit Kamm, Patrick R. Gruber & Michael Kamm eds., 2006).

All the above patents and publications are incorporated by reference in their entirety.

SUMMARY OF THE INVENTION

In certain embodiments, the fatty acyl moieties of the triglyceride may include palmitoleic acyl, oleic acyl, linoleic acyl, linolenic acyl, alpha-eleostearic acyl, ricinoleic acyl, gadoleic acyl, arachidonic acyl, cetoleic acyl, or erucic acyl. The triglyceride may be soybean oil triglyceride, canola oil triglyceride, high oleic canola oil triglyceride, cottonseed oil triglyceride, rapeseed oil triglyceride, palm oil triglyceride, a triglyceride of palm oil fractions, corn oil triglycerides, triglycerides made from fatty acids and glycerol such as glycerol trioleate made from distilled tall oil, or a combination of two or more of these. Partially hydrogenated forms of any of the above oil triglycerides may also be used. The carboxylic acid may be acetic acid, propanoic acid, butanoic acid, pentanoic acid, or hexanoic acid or a combination of two or more of these. The reaction is carried out in the presence of a metal ion or other electron acceptor.

Certain embodiments provide a method for modifying ethylenic unsaturation in a triglyceride. A triglyceride having at least one fatty acyl moiety with a site of unsaturation is reacted with a ketone, thereby substituting a ketone moiety for at least one site of unsaturation in a fatty acyl moiety of the triglyceride.

In certain embodiments, the fatty acyl moieties of the triglyceride may include palmitoleic acyl, oleic acyl, linoleic acyl, linolenic acyl, alpha-eleostearic acyl, ricinoleic acyl, gadoleic acyl, arachidonic acyl, cetoleic acyl, or erucic acyl. The triglyceride may be soybean oil triglyceride, canola oil triglyceride, high oleic canola oil triglyceride, cottonseed oil triglyceride, rapeseed oil triglyceride, palm oil triglyceride, a triglyceride of palm oil fractions, corn oil triglycerides, triglycerides made from fatty acids and glycerol such as glycerol trioleate made from distilled tall oil, or a combination of two or more of these. Partially hydrogenated forms of any of the above oil triglycerides may also be used. The ketone may be acetone, pentane-2,4-dione, benzophenone, cyclohexanone, diacetone alcohol, diisobutyl ketone, isophorone, methyl amyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isobutyl ketone, or a combination of two or more of these. The reaction is carried out in the presence of a metal ion or other electron acceptor.

The triglycerides of certain embodiments may be useful as lubricants, hydraulic fluids, dielectric fluids, including dielectric cooling fluids, or intermediates for polymer synthesis.

BRIEF DESCRIPTION OF DRAWING FIGURES

FIG. 1 shows a reaction of an olefin with a carboxylic acid having two or more carbon atoms to form an analog of the olefin having a lactone ring in place of a site of ethylenic unsaturation in a fatty acid. The assignment of “R” moieties from the reactants in the product is contemplated to be correct, but the invention is not limited according to the accuracy of these assignments.

FIG. 2 shows a reaction of an olefin with a ketone moiety to form an analog of the olefin having a pendant ketone group in place of a site of ethylenic unsaturation in a fatty acid and a carboxylate group in place of a site of ethylenic unsaturation in the fatty acid. The assignment of “R” moieties from the reactants in the product is contemplated to be correct, but the invention is not limited according to the accuracy of these assignments.

DETAILED DESCRIPTION OF THE INVENTION

Certain embodiments provide a method for modifying unsaturated vegetable oils to improved certain properties, such as oxidative stability. Certain embodiments include vegetable oils modified with lactone, ketone, or vinyl moieties and having improved oxidative stability over the unmodified oil. Sites of ethylenic unsaturation in vegetable oils are prone to oxidative degradation. These same sites will preferentially react via free radical chemistry as compared to saturated sites in vegetable oils. Without being bound by a particular theory, it is contemplated that unsaturated sites separated by a methylene group are more oxidatively reactive than isolated unsaturated sites. Certain embodiments take advantage of the preferential reactivity present in the unsaturated fatty acyl moieties of vegetable oils to improve the oxidative stability of those vegetable oils.

In certain embodiments, a lactone structure is contemplated in which a lactone moiety is substituted for at least one, alternatively two, alternatively three, alternatively four, alternatively five, alternatively six, alternatively all, of the ethylenic double bonds on at least one fatty acid chain of an unsaturated fatty acyl moiety of a free fatty acid, glyceride or other ester.

Alternatively, lactone compounds made by any process and having the formula set forth as the bottom structure of FIG. 1 are contemplated. In this structure and the other structures of FIG. 1, R¹ and R³ can be, for example, independently hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, or t-butyl. At least one of R2 and R4 can be, for example, a straight or branched acyl moiety having predominantly from 1-22 carbon atoms, alternatively predominantly from 4-20 carbon atoms, alternatively predominantly from 6-18 carbon atoms, alternatively predominantly from 12-14 carbon atoms, with a hydroxyl or ester terminal group (where R is a hydrocarbon). The other of R2 and R4 can be an acyl moiety with a hydroxyl terminal group or ester linkage as just described or hydrogen. R5 and R6 can be independently any of the previously mentioned alternatives for R1-R4.

Alternatively, an embodiment according to the bottom structure in FIG. 1 is contemplated which is the partial or complete lactone analog of the olefin defined by the top structure of FIG. 1. In this embodiment, the olefin at the top of FIG. 1 is alternatively palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, alpha-eleostearic acid, ricinoleic acid, gadoleic acid, arachidonic acid, cetoleic acid, erucic acid, or any of the unsaturated acids shown in KIRK-OTHMER, ENCYCLOPEDIA OF SCIENCE AND TECHNOLOGY, 4^(th) Ed., Vol. 10, page 254, which is incorporated by reference, or any combination of two or more of these. The lactone may be oriented as illustrated or in a flipped orientation in which R¹ and R³ are switched and R2 and R4 are switched. A lactone moiety can be substituted for one, alternatively two, alternatively three, alternatively four, alternatively five, alternatively six, alternatively all, of the ethylenic double bonds on at least one fatty acid chain of an unsaturated fatty acyl moiety of a free fatty acid, glyceride or other ester. The free fatty acid, glyceride, or other ester can be any material known for use as a lubricant, alone or in combination with other ingredients.

Alternatively the invention is the modification of soybean oil by substitution of a lactone ring for one, two, or three ethylenic double bonds per fatty acyl moiety. For example, a linolenic acyl moiety of a soybean oil triglyceride (which is unsaturated at the 9, 12, and 15 positions) is modified by converting the ethylenic double bond at the 15 position to a lactone ring, as shown in FIG. 1. Either that mono-substituted linolenic acyl or linoleic acyl, either of which has ethylenic unsaturation at the 9 and 12 positions, can be reacted as shown in FIG. 1 by converting the ethylenic double bond at the 12 position to a lactone ring. Either that di-substituted linolenic acyl, that monosubstituted linoleic acyl, or oleic acyl, any of which has ethylenic unsaturation at the 9 position, can be reacted as shown in FIG. 1 by converting the ethylenic double bond at the 9 position to a lactone ring, leaving a saturated acyl moiety with one, two, or three lactone rings, respectively.

In certain embodiments, a ketone structure is contemplated in which a ketone moiety is substituted for at least one, alternatively two, alternatively three, alternatively four, alternatively five, alternatively six, alternatively all, of the ethylenic double bonds on at least one fatty acid chain of an unsaturated fatty acyl moiety of a free fatty acid, glyceride or other ester.

Alternatively, a ketone structure is contemplated in which a ketone moiety and a carboxylate moiety are each substituted for at least one, alternatively two, alternatively three, alternatively four, alternatively five, alternatively six, alternatively half of all, of the ethylenic double bonds on at least one fatty acid chain of an unsaturated fatty acyl moiety of a free fatty acid, glyceride or other ester.

Alternatively, ketone compounds made by any process and having the formula set forth as the reaction product of FIG. 2 are contemplated. In this structure and the other structures of FIG. 2, R¹ and R³ can be, for example, independently hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, or t-butyl. At least one of R2 and R4 can be, for example, a straight or branched acyl moiety having predominantly from 1-22 carbon atoms, alternatively predominantly from 4-20 carbon atoms, alternatively predominantly from 6-18 carbon atoms, alternatively predominantly from 12-14 carbon atoms, with a hydroxyl or ester terminal group (where R is a hydrocarbon). The other of R2 and R4 can be an acyl moiety with a hydroxyl terminal group or ester linkage as just described or hydrogen. R5 can be any of the previously mentioned alternatives for R1-R4.

Alternatively, an embodiment according to the reaction product in FIG. 2 is contemplated which is the partial or complete ketone analog of the olefin of FIG. 2. In this embodiment, the olefin of FIG. 2 is alternatively palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, alpha-eleostearic acid, ricinoleic acid, gadoleic acid, arachidonic acid, cetoleic acid, erucic acid, or any of the unsaturated acids shown in KIRK-OTHMER, ENCYCLOPEDIA OF SCIENCE AND TECHNOLOGY, 4^(th) Ed., Vol. 10, page 254 or any combination of two or more of these. The ketone product may be oriented as illustrated or in a flipped orientation in which R¹ and R³ are switched and R2 and R4 are switched. A ketone moiety can be substituted for one, alternatively two, alternatively three, alternatively four, alternatively five, alternatively six, alternatively all, of the ethylenic double bonds on at least one fatty acid chain of an unsaturated fatty acyl moiety of a free fatty acid, glyceride or other ester. Alternatively, a ketone structure is contemplated in which a ketone moiety and a carboxylate moiety are each substituted for at least one, alternatively two, alternatively three, alternatively four, alternatively five, alternatively six, alternatively half of all, of the ethylenic double bonds on at least one fatty acid chain of an unsaturated fatty acyl moiety of a free fatty acid, glyceride or other ester. The free fatty acid, glyceride, or other ester can be any material known for use as a lubricant, alone or in combination with other ingredients.

Alternatively the invention is the modification of soybean oil by substitution of a ketone moiety for one, two, or three ethylenic double bonds per fatty acyl moiety. For example, a linolenic acyl moiety of a soybean oil triglyceride (which is unsaturated at the 9, 12, and 15 positions) is modified by converting the ethylenic double bond at the position to a pendant ketone moiety, as shown in FIG. 2. Either that mono-substituted linolenic acyl or linoleic acyl, either of which has ethylenic unsaturation at the 9 and 12 positions, can be reacted as shown in FIG. 2 by converting the ethylenic double bond at the 12 position to a pendant ketone moiety. Either that di-substituted linolenic acyl, that monosubstituted linoleic acyl, or oleic acyl, any of which has ethylenic unsaturation at the 9 position, can be reacted as shown in FIG. 2 by converting the ethylenic double bond at the 9 position to a pendant ketone moiety, leaving a saturated acyl moiety with one, two, or three ketone moieties, respectively, and one, two or three other moieties, such as carboxylate moieties, respectively.

In certain embodiments, a vinyl structure is contemplated in which a vinyl moiety is substituted for at least one, alternatively two, alternatively three, alternatively four, alternatively five, alternatively six, alternatively all, of the ethylenic double bonds on at least one fatty acid chain of an unsaturated fatty acyl moiety of a free fatty acid, glyceride or other ester.

Alternatively, an embodiment is contemplated which is the partial or complete vinyl analog of an olefin. In this embodiment, the olefin is alternatively palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, alpha-eleostearic acid, ricinoleic acid, gadoleic acid, arachidonic acid, cetoleic acid, erucic acid, or any of the unsaturated acids shown in KIRK-OTHMER, ENCYCLOPEDIA OF SCIENCE AND TECHNOLOGY, 4^(th) Ed., Vol. 10, page 254 or any combination of two or more of these. A vinyl moiety can be substituted for one, alternatively two, alternatively three, alternatively four, alternatively five, alternatively six, alternatively all, of the ethylenic double bonds on at least one fatty acid chain of an unsaturated fatty acyl moiety of a free fatty acid, glyceride or other ester. The free fatty acid, glyceride, or other ester can be any material known for use as a lubricant, alone or in combination with other ingredients.

Alternatively the invention is the modification of soybean oil by substitution of a vinyl moiety for one, two, or three ethylenic double bonds per fatty acyl moiety. For example, a linolenic acyl moiety of a soybean oil triglyceride (which is unsaturated at the 9, 12, and 15 positions) is modified by converting the ethylenic double bond at the 15 position to a pendant vinyl moiety. Either that mono-substituted linolenic acyl or linoleic acyl, either of which has ethylenic unsaturation at the 9 and 12 positions, can be reacted by converting the ethylenic double bond at the 12 position to a pendant vinyl moiety. Either that di-substituted linolenic acyl, that monosubstituted linoleic acyl, or oleic acyl, any of which has ethylenic unsaturation at the 9 position, can be reacted by converting the ethylenic double bond at the 9 position to a pendant vinyl moiety, leaving a saturated acyl moiety with one, two, or three vinyl moieties, respectively.

The triglyceride oils have the formula:

In this formula, R⁷, R⁸, and R⁹ are independently any fatty acyl moiety corresponding to one of the fatty acids listed in the Kirk-Othmer table incorporated by reference, with the restriction that at least one of R⁷, R⁸, and R⁹ is an ethylenically unsaturated acyl moiety available for lactone substitution. The carbonyl moieties of R⁷, R⁸, and R⁹ are linked to the respective oxygen atoms of the nucleus shown above to form ester linkages. Each triglyceride has three fatty acyl groups, so a large number of different triglyceride species are present in a natural triglyceride oil.

Alternatively, R⁷, R⁸, and R⁹ are predominantly acyls of any of the most abundant fatty acids, which are stearic acid, oleic acid, linoleic acid, linolenic acid, and palmitoleic acid. Of these, stearic acid has no ethylenic double bonds, and the others have one ethylenic double bond (oleic and palmitoleic acids), two ethylenic double bonds (linoleic acid), or three ethylenic double bonds (linolenic acid). The combinations of R⁷, R⁸, and R⁹ on the most abundant species of triglycerides in soybean oil are provided in the table of triglyceride acyls.

TABLE 1 Triglyceride Acyls Glyceride Species R⁷ R⁸ R⁹ 1. stearic acyl stearic acyl palmitoleic acyl 2. stearic acyl stearic acyl oleic acyl 3. stearic acyl stearic acyl linoleic acyl 4. stearic acyl stearic acyl linolenic acyl 5. stearic acyl palmitoleic acyl palmitoleic acyl 6. stearic acyl palmitoleic acyl oleic acyl 7. stearic acyl palmitoleic acyl linoleic acyl 8. stearic acyl palmitoleic acyl linolenic acyl 9. stearic acyl oleic acyl oleic acyl 10. stearic acyl oleic acyl linoleic acyl 11. stearic acyl oleic acyl linolenic acyl 12. stearic acyl linoleic acyl linoleic acyl 13. stearic acyl linoleic acyl linolenic acyl 14. stearic acyl linolenic acyl linolenic acyl 15. palmitoleic acyl palmitoleic acyl palmitoleic acyl 16. palmitoleic acyl palmitoleic acyl oleic acyl 17. palmitoleic acyl palmitoleic acyl linoleic acyl 18. palmitoleic acyl palmitoleic acyl linolenic acyl 19. palmitoleic acyl oleic acyl oleic acyl 20. palmitoleic acyl oleic acyl linoleic acyl 21. palmitoleic acyl oleic acyl linolenic acyl 22. palmitoleic acyl linoleic acyl linolenic acyl 23. palmitoleic acyl linolenic acyl linolenic acyl 24. oleic acyl oleic acyl oleic acyl 25. oleic acyl oleic acyl linoleic acyl 26. oleic acyl oleic acyl linolenic acyl 27. oleic acyl linoleic acyl linoleic acyl 28. oleic acyl linoleic acyl linolenic acyl 29. oleic acyl linolenic acyl linolenic acyl 30. linoleic acyl linoleic acyl linoleic acyl 31. linoleic acyl linoleic acyl linolenic acyl 32. linoleic acyl linolenic acyl linolenic acyl 33. linolenic acyl linolenic acyl linolenic acyl

The triglycerides are reacted as described in this specification to substitute a lactone, ketone, or vinyl moiety for one or more ethylenic double bonds. It is contemplated that, for a particular fatty acyl moiety having more than one site of unsaturation, the lactone, ketone, or vinyl substitution can be partial or complete. It is contemplated that the first site that will be substituted is the highest-numbered site of unsaturation, and additional sites will be substituted in descending numerical order. It is further contemplated that, when a triglyceride having two or three different types of unsaturated acyl moieties is reacted to substitute lactone, ketone, or vinyl moieties for ethylenic double bonds, assuming enough of the substituent reactant and any necessary catalyst is present, identically numbered sites of unsaturation generally will be in the same state (either substituted or unsubstituted) after the reaction, although the invention is not limited to instances in which this is the case.

The oils contemplated for use in the reactions described herein include soybean oil, canola oil, high oleic canola oil, cottonseed oil, rapeseed oil, palm oil, palm oil fraction, corn oil triglycerides, triglycerides made from fatty acids and glycerol such as glycerol trioleate made from distilled tall oil, or a combination of two or more of these. Partially hydrogenated forms of any of the above oil triglycerides may also be used.

The acids contemplated for use in the lactone reaction include any carboxylic acid having two or more carbon atoms, for example, acetic, propanoic, butanoic, pentanoic, and hexanoic acid.

The ketones contemplated for use in the ketone reaction include any ketone having two or more carbon atoms, for example, acetone, pentane-2,4-dione, benzophenone, cyclohexanone, diacetone alcohol, diisobutyl ketone, isophorone, methyl amyl ketone, methyl ethyl ketone, methyl isoamyl ketone, and methyl isobutyl ketone.

The metal ions contemplated for use in the lactone reaction include an ion of manganese (Mn), vanadium (V), cerium or Ce, with any suitable anion or combination of anions. One contemplated anion is a deprotonated carboxylic acid (i.e. carboxyl) moiety. While metal ions are preferred for certain embodiments, the reactions contemplated may be carried out in the presence of any suitable electron acceptor.

The most common reaction products of the various substitution reactions (lactone, ketone, and/or vinyl) carried out on a homogeneous triglyceride (i.e. R⁷, R⁸, and R⁹ are the same fatty acyl moiety) or heterogeneous triglyceride (i.e. R⁷, R⁸, and R⁹ are two or three different fatty acyl moieties) are summarized in the Table of Reaction Products, in which each combination of R⁷, R⁸, and R⁹ according to the above triglyceride structure is presented as one of the rows in the table.

TABLE 2 Reaction Products Glyc- eride Species R⁷ R⁸ R⁹ 34. stearic acyl stearic acyl palmitoleic acyl with a substitution at the 9 position 35. stearic acyl stearic acyl oleic acyl with a substitution at the 9 position 36. stearic acyl stearic acyl linoleic acyl with a substitution at the 12 position 37. stearic acyl stearic acyl linoleic acyl with substitutions at the 9 and 12 positions 38. stearic acyl stearic acyl linolenic acyl with a substitution at the 15 position 39. stearic acyl stearic acyl linolenic acyl with substitutions at the 12 and 15 positions 40. stearic acyl stearic acyl linolenic acyl with substitutions at the 9, 12 and 15 positions 41. stearic acyl palmitoleic acyl palmitoleic acyl with a substitution with a substitution at the 9 position at the 9 position 42. stearic acyl palmitoleic acyl oleic acyl with a with a substitution substitution at the at the 9 position 9 position 43. stearic acyl palmitoleic acyl linoleic acyl with a substitution at the 12 position 44. stearic acyl palmitoleic acyl linoleic acyl with with a substitution substitutions at at the 9 position the 9 and 12 positions 45. stearic acyl palmitoleic acyl linolenic acyl with a substitution at the 15 position 46. stearic acyl palmitoleic acyl linolenic acyl with substitutions at the 12 and 15 positions 47. stearic acyl palmitoleic acyl linolenic acyl with with a substitution substitutions at at the 9 position the 9, 12 and 15 positions 48. stearic acyl oleic acyl with a oleic acyl with a substitution at the substitution at the 9 position 9 position 49. stearic acyl oleic acyl linoleic acyl with a substitution at the 12 position 50. stearic acyl oleic acyl with a linoleic acyl with substitution at the substitutions at 9 position the 9 and 12 positions 51. stearic acyl oleic acyl linolenic acyl with a substitution at the 15 position 52. stearic acyl oleic acyl linolenic acyl with I substitutions at the 12 and 15 positions 53. stearic acyl oleic acyl with a linolenic acyl with substitution at the substitutions at 9 position the 9, 12 and 15 positions 54. stearic acyl linoleic acyl with a linoleic acyl with a substitution at the substitutions at 12 position the 12 position 55. stearic acyl linoleic acyl with linoleic acyl with substitutions at substitutions at the 9 and 12 the 9 and 12 positions positions 56. stearic acyl linoleic acyl linolenic acyl with a substitution at the 15 position 57. stearic acyl linoleic acyl with a linolenic acyl with substitution at the substitutions at 12 position the 12 and 15 positions 58. stearic acyl linoleic acyl with linolenic acyl with substitutions at substitutions at the 9 and 12 the 9, 12 and 15 positions positions 59. stearic acyl linolenic acyl with linolenic acyl with a substitution at a substitution at the 15 position the 15 position 60. stearic acyl linolenic acyl with linolenic acyl with substitutions at substitutions at the 12 and 15 the 12 and 15 positions positions 61. stearic acyl linolenic acyl with linolenic acyl with substitutions at substitutions at the 9, 12 and 15 the 9, 12 and 15 positions positions 62. palmitoleic acyl palmitoleic acyl palmitoleic acyl with a substitution with a substitution at the 9 position at the 9 position 63. palmitoleic acyl palmitoleic acyl oleic acyl with a with a substitution with a substitution substitution at the at the 9 position at the 9 position 9 position 64. palmitoleic acyl palmitoleic acyl linoleic acyl with a substitution at the 12 position 65. palmitoleic acyl palmitoleic acyl linoleic acyl with with a substitution with a substitution substitutions at at the 9 position at the 9 position the 9 and 12 positions 66. palmitoleic acyl palmitoleic acyl linolenic acyl with a substitution at the 15 position 67. palmitoleic acyl palmitoleic acyl linolenic acyl with substitutions at the 12 and 15 positions 68. palmitoleic acyl palmitoleic acyl linolenic acyl with with a substitution with a substitution substitutions at at the 9 position at the 9 position the 9, 12 and 15 positions 69. palmitoleic acyl oleic acyl with a oleic acyl with a with a substitution substitution at the substitutions at at the 9 position 9 position the 9 position 70. palmitoleic acyl oleic acyl linoleic acyl with a substitution at the 12 position 71. palmitoleic acyl oleic acyl with a linoleic acyl with with a substitution substitution at the substitutions at at the 9 position 9 position the 9 and 12 positions 72. palmitoleic acyl oleic acyl linolenic acyl with a substitution at the 15 position 73. palmitoleic acyl oleic acyl linolenic acyl with substitutions at the 12 and 15 positions 74. palmitoleic acyl oleic acyl with a linolenic acyl with with a substitution substitution at the substitutions at at the 9 position 9 position the 9, 12 and 15 positions 75. palmitoleic acyl linoleic acyl linolenic acyl with a substitution at the 15 position 76. palmitoleic acyl linoleic acyl with a linolenic acyl with substitution at the substitutions at 12 position the 12 and 15 positions 77. palmitoleic acyl linoleic acyl with linolenic acyl with with a substitution substitutions at substitutions at at the 9 position the 9 and 12 the 9, 12 and 15 positions positions 78. palmitoleic acyl linolenic acyl with linolenic acyl with a substitution at a substitution at the 15 position the 15 position 79. palmitoleic acyl linolenic acyl with linolenic acyl with substitutions at substitutions at the 12 and 15 the 12 and 15 positions positions 80. palmitoleic acyl linolenic acyl with linolenic acyl with with a substitution substitutions at substitutions at at the 9 position the 9, 12 and 15 the 9, 12 and 15 positions positions 81. oleic acyl with a oleic acyl with a oleic acyl with a substitution at the substitution at the substitution at the 9 position 9 position 9 position 82. oleic acyl oleic acyl linoleic acyl with a substitution at the 12 position 83. oleic acyl with a oleic acyl with a linoleic acyl with substitution at the substitution at the substitutions at 9 position 9 position the 9 and 12 positions 84. oleic acyl oleic acyl linolenic acyl with a substitution at the 15 position 85. oleic acyl oleic acyl linolenic acyl with substitutions at the 12 and 15 positions 86. oleic acyl with a oleic acyl with a linolenic acyl with substitution at the substitution at the substitutions at 9 position 9 position the 9, 12 and 15 positions 87. oleic acyl linoleic acyl with a linoleic acyl with a substitution at the substitution at the 12 position 12 position 88. oleic acyl with a linoleic acyl with linoleic acyl with substitution at the substitutions at substitutions at 9 position the 9 and 12 the 9 and 12 positions positions 89. oleic acyl linoleic acyl linolenic acyl with a substitution at the 15 position 90. oleic acyl linoleic acyl with a linolenic acyl with substitution at the substitutions at 12 position the 12 and 15 positions 91. oleic acyl with a linoleic acyl with linolenic acyl with substitution at the substitutions at substitutions at 9 position the 9 and 12 the 9, 12 and 15 positions positions 92. oleic acyl linolenic acyl with linolenic acyl with a substitution at a substitution at the 15 position the 15 position 93. oleic acyl linolenic acyl with linolenic acyl with substitutions at substitutions at the 12 and 15 the 12 and 15 positions positions 94. oleic acyl with a linolenic acyl with linolenic acyl with substitution at the substitutions at substitutions at 9 position the 9, 12 and 15 the 9, 12 and 15 positions positions 95. linoleic acyl with a linoleic acyl with a linoleic acyl with a substitution at the substitution at the substitution at the 12 position 12 position 12 position 96. linoleic acyl with linoleic acyl with linoleic acyl with substitutions at substitutions at substitutions at the 9 and 12 the 9 and 12 the 9 and 12 positions positions positions 97. linoleic acyl linoleic acyl linolenic acyl with a substitution at the 15 position 98. linoleic acyl with a linoleic acyl with a linolenic acyl with substitution at the substitution at the substitutions at 12 position 12 position the 12 and 15 positions 99. linoleic acyl with linoleic acyl with linolenic acyl with substitutions at substitutions at substitutions at the 9 and 12 the 9 and 12 the 9, 12 and 15 positions positions positions 100. linoleic acyl linolenic acyl with linolenic acyl with a substitution at a substitution at the 15 position the 15 position 101. linoleic acyl with a linolenic acyl with linolenic acyl with substitution at the substitutions at substitutions at 12 position the 12 and 15 the 12 and 15 positions positions 102. linoleic acyl with linolenic acyl with linolenic acyl with substitutions at substitutions at substitutions at the 9 and 12 the 9, 12 and 15 the 9, 12 and 15 positions positions positions 103. linolenic acyl with linolenic acyl with linolenic acyl with a substitution at a substitution at a substitution at the 15 position the 15 position the 15 position 104. linolenic acyl with linolenic acyl with linolenic acyl with substitutions at substitutions at substitutions at the 12 and 15 the 12 and 15 the 12 and 15 positions positions positions 105. linolenic acyl with linolenic acyl with linolenic acyl with substitutions at substitutions at substitutions at the 9, 12 and 15 the 9, 12 and 15 the 9, 12 and 15 positions positions positions

It is contemplated that in certain embodiments, the substituted structures are more stable to oxidation than the double bond. In certain embodiments, the lactone ring structure, the ketone pendant group, and the pendant vinyl group inhibit crystallization of the oil. Differential scanning calorimetry (DSC) data, discussed more fully in the examples below, indicates that with increasing level of treatment the lactone and ketone reaction products show reduced crystallinity. Measuring the area under the DSC curve is useful for determining the extent of crystallinity. The invention is not, however, limited to embodiments having these properties.

It is contemplated that in certain embodiments, an unsaturated free fatty acid or acyl moiety is modified to reduce the amount of unsaturation by reacting an ethylenic double bond to produce a lactone structure on the fatty acid chain. Such lactone structures on fatty acid chains have been successfully produced using both a fatty acid mixture that is mainly oleic acid and soybean oil as starting materials. Analysis of the reacted fatty acid mixture or with the reacted soybean oil shows that the fatty acid composition as determined by gas chromatography (GC) analysis of methyl esters has changed compared to the starting material. It is contemplated that this change includes reformation of an ethylenic double bond as a linked-in lactone ring in the hydrocarbon chain of the acyl moiety.

It is also contemplated to modify any unsaturated free fatty acid by conversion of some or all of its ethylenic double bonds to lactone rings, and then make esters with the lactone intermediates to gain the benefits of this approach to stabilizing triglycerides or esters to oxidation.

It is also contemplated to modify any unsaturated fatty acyl moiety of a triglyceride by conversion of some or all of its ethylenic double bonds to lactone rings, and then split off free fatty acids to gain the benefits of this approach to stabilizing triglycerides or esters to reduce oxidation.

It is further contemplated to prepare a lactone analog of any lubricant species containing ethylenic unsaturation, either by reacting the lubricant species directly or by reacting a precursor having ethylenic unsaturation as described here with a carboxylic acid as described here in the presence of a metal ion or other electron acceptor.

This development is contemplated to allow one or both of the two principal shortcomings of vegetable oils in terms of many industrial uses, relatively low oxidative stability and relatively high pour points, to be addressed with a single reaction chemistry that is easy to carry out and uses relatively low cost reactants. The degree of modification of the starting material can be tailored to match the end use of the product.

One method of characterizing oxidative stability is known as thin film micro-oxidation (TFMO). An example of this method is provided in W. Castro, J. M. Erhan, S. Z. Erhan and F. Caputo, A Study of the Oxidation and Wear Properties of Vegetable Oils Soybean Oil without Additives, J. AMER. OIL. CHEM. SOC., 83(1) 2006 p. 47-52, which is incorporated by reference in its entirety.

To characterize the oxidative stability of the reaction products described herein, the above method has been modified somewhat. Briefly, the subject oil is applied by micropipette to a weighing pan for a microbalance to create a thin film and weighed. The weighed pan is placed in clean glass reaction tubes. The tubes are placed in a heating block with an air flow of approximately 20 ml/min being maintained over the oil sample. The oil sample is heated for a given time, such a 30 minutes, 60 minutes, 90 minutes or 120 minutes, and given temperature, such as 150° C., 175° C., or 200° C. The pans containing the oil samples are allowed to cool and then weighed. The difference between the original sample weight and the sample weight after heating is the evaporation loss, which can be expressed as a percentage called percent volatiles. The pans containing the oxidized samples are then washed in an organic solvent such as tetrahydrofuran (THF) to remove soluble oil. Other solvents could be used. The pans, with depositing remaining on them after the washing step, are placed in a dessicator to dry. Once dry, the pans are again weighed. From the difference between the original sample weight and the sample weight after washing, one can determine the weight of the deposits left in the pan, which can be expressed as a percentage called percent deposits.

The free radical chemistry is contemplated to react more strongly with polyunsaturated fatty acids than with monounsaturated fatty acids so the modification tends to target the formation of reaction products in a way to get the greatest benefit for any given level of treatment.

The present reaction products are contemplated to be useful and to achieve a technical effect as lubricants, or as ingredients of a lubricant formulation. Alternatively, the present reaction products are contemplated to be useful and to achieve a technical effect as hydraulic fluids, or as ingredients of a hydraulic fluid formulation. Alternatively, the present reaction products are contemplated to be useful and to achieve a technical effect as dielectric fluids, including dielectric cooling fluids, or as ingredients of a dielectric fluid formulation.

It is further contemplated that after running the lactone, ketone, or vinyl reactions, the resulting products could be hydrogenated to remove residual double bonds in the fatty acid chains. Hydrogenation of the ketone reaction products is contemplated to lead to useful polyol intermediates for other reaction chemistries. Alternatively, hydrogenation of the reaction products of certain embodiments of the vinyl grafting chemistry is contemplated to lead to a highly stable final product if no additional oxygen atoms are added to the final reaction products in the form of a carbonyl, ester, or hydroxyl group.

It is further contemplated that the ketone structure of certain embodiments provide a way for further modification of the ketone chemistry reaction products by incorporating a hydroxyl group. Hydroxyl groups may be provided in certain embodiments by running the reaction in the presence of water. A hydroxyl group provides a novel path to polyol production from vegetable oils. Vegetable based polyols are contemplated to be useful in the manufacture of biologically-based polyurethane polymers. Further, reacting the hydroxyl group via an ester linkage may be used to form further appendages. Vegetable based polyols produced in accordance with certain embodiments of the ketone chemistry may behave as emulsifiers depending upon the average number of hydroxyl groups per triglyceride molecule.

The following examples are provided to illustrate the invention and how to practice it. The scope of the invention is not limited by these examples or the remainder of the specification, but is defined solely by the claims.

EXAMPLE 1 Preparation of Mn⁺³

78.1 g. Mn₂O₃ is placed in a 1-liter reactor, which is then rinsed down with 28.3 g. glacial acetic acid. 151.5 g. acetic anhydride are added, forming a black slurry. An additional 236.8 g. glacial acetic acid is added, and the mixture is allowed to stand for about four hours at room temperature. The reaction mixture is then heated using an electric heater, gradually raising its temperature to 104° C. after about three hours. The temperature remains at 104° C. for an additional 45 minutes, after which the heat is turned off and the mixture is allowed to cool overnight. The product is contemplated to contain:

(Mn(OAc)₃) in acetic anhydride, which is referred to in this specification as an Mn⁺³ mixture. In the above formula, three deprotonated carboxylic acid moieties are anions associated with the Mn cation.

EXAMPLE 2 Conversion of Olefin to Lactone

20.0 g. of acetic acid are added to 100.0 g. of soybean oil. 16.1 g. of the Mn+³ mixture produced in Example 1 is added. The reaction mixture is heated to 50° C., then allowed to cool to ambient room temperature for 12 hours. The product is contemplated to contain a triglyceride in which lactone moieties are formed at the sites of at least some of the olefinic double bonds. A sample is taken, then this product is heated in a glass double boiler to 70° C.-80° C. and held for one hour at that temperature. The product is then allowed to cool to room temperature. The product is contemplated to contain a triglyceride in which lactone moieties are formed at the sites of at least some of the olefinic double bonds.

EXAMPLE 3 Conversion of Olefin to Lactone

16.0 g. of the Mn⁺³ mixture produced in Example 1 is heated to 50° C., then added to 100 g. of soybean oil held at room temperature. The product is contemplated to contain a triglyceride in which lactone moieties are formed at the sites of at least some of the olefinic double bonds.

EXAMPLE 4 Different Lactone Species

The reaction of each preceding example is repeated multiple times, using as the olefin in different trials: 1-dodecene, 90% oleic acid, low saturated soy acids, soy oil, and 1 g. of each of the preceding olefins combined with 1 g. of water. The successful reaction products are shown by gas chromatography to be different from the reactants. The products are contemplated to be the lactones indicated in FIG. 1.

EXAMPLE 5 Soybean Oil with Lactone Modification

27.0 g. Mn(OAc)₂.4H₂O. and 139.5 g. of acetic acid are mixed in a reaction vessel. 4.1 g. of KMnO₄ is added. 48.1 g. acetic anhydride is added. 25.1 g. of a refined, bleached and deodorized soybean oil (sold under the trademark IMPERIAL VEGETABLE OIL®) is added to the vessel, which is heated and allowed to cool. The reaction undergoes a series of color changes over time. A precipitate collects at the bottom of the vessel. The reaction product is referred to in this specification as 1757.

EXAMPLE 6 Soybean Oil with Ketone Modification

27.0 g. Mn(OAc)₂.4H₂O. and 139.9 g. of acetic acid are mixed in a reaction vessel. 4.1 g. of KMnO₄ is added. 48.4 g. acetic anhydride is added. 25.1 g. of a refined, bleached and deodorized soybean oil and 200 ml of acetone are added to the vessel, which is heated and allowed to cool. The reaction undergoes a series of color changes over time. A precipitate collects at the bottom of the vessel. The reaction product is referred to in this specification as 1756.

EXAMPLE 7 Soybean Oil with Lactone Modification

27.0 g. Mn(OAc)₂.4H₂O. and 139.7 g. of acetic acid are mixed in a reaction vessel. 4.1 g. of KMnO₄ is added. 49.2 g. acetic anhydride is added. 7.6 g. of a refined, bleached and deodorized soybean oil is added to the vessel, which is heated and allowed to cool. The reaction undergoes a series of color changes over time. A precipitate collects at the bottom of the vessel. The reaction product is referred to in this specification as 0458.

EXAMPLE 8 Soybean Oil with Ketone Modification

27.0 g. Mn(OAc)₂.4H₂O. and 139.5 g. of acetic acid are mixed in a reaction vessel. 4.1 g. of KMnO₄ is added. 47.7 g. acetic anhydride is added. 7.5 g. of a refined, bleached and deodorized soybean oil and 200 ml of acetone are added to the vessel, which is heated and allowed to cool. The reaction undergoes a series of color changes over time. A precipitate collects at the bottom of the vessel. The reaction product is referred to in this specification as 0459.

EXAMPLE 9 Partially Hydrogenated Soybean Oil with Lactone Modification

27.0 g. Mn(OAc)₂.4H₂O. and 139.5 g. of acetic acid are mixed in a reaction vessel. 4.1 g. of KMnO₄ is added. 47.8 g. acetic anhydride is added. 12.0 g. of a refined, bleached and partially hydrogenated soybean oil is added to the vessel, which is heated and allowed to cool. The reaction undergoes a series of color changes over time. A precipitate collects at the bottom of the vessel. The reaction product is referred to in this specification as 1085.

EXAMPLE 10 Partially Hydrogenated Soybean Oil with Ketone Modification

27.0 g. Mn(OAc)₂.4H₂O. and 139.5 g. of acetic acid are mixed in a reaction vessel. 4.1 g. of KMnO₄ is added. 47.9 g. acetic anhydride is added. 12.0 g. of a refined, bleached and partially hydrogenated soybean oil and 200 ml of acetone are added to the vessel, which is heated and allowed to cool. The reaction undergoes a series of color changes over time. A precipitate collects at the bottom of the vessel. The reaction product is referred to in this specification as 1086.

EXAMPLE 11 Partially Hydrogenated Soybean Oil with Lactone Modification

27.0 g. Mn(OAc)₂.4H₂O. and 139.6 g. of acetic acid are mixed in a reaction vessel. 4.1 g. of KMnO₄ is added. 47.6 g. acetic anhydride is added. 23.6 g. of a refined, bleached and partially hydrogenated soybean oil is added to the vessel, which is heated and allowed to cool. The reaction undergoes a series of color changes over time. A precipitate collects at the bottom of the vessel. The reaction product is referred to in this specification as 0823.

EXAMPLE 12 Partially Hydrogenated Soybean Oil with Ketone Modification

27.0 g. Mn(OAc)₂.4H₂O. and 139.5 g. of acetic acid are mixed in a reaction vessel. 4.1 g. of KMnO₄ is added. 48.0 g. acetic anhydride is added. 23.6 g. of a refined, bleached and partially hydrogenated soybean oil and 200 ml of acetone are added to the vessel, which is heated and allowed to cool. The reaction undergoes a series of color changes over time. A precipitate collects at the bottom of the vessel. The reaction product is referred to in this specification as 0824.

EXAMPLE 13 High Oleic Canola Oil with Lactone Modification

27.0 g. Mn(OAc)₂.4H₂O. and 139.5 g. of acetic acid are mixed in a reaction vessel. 4.1 g. of KMnO₄ is added. 47.7 g. acetic anhydride is added. 8.8 g. of a refined, bleached and deodorized high oleic canola oil (sold under the trademark NUTRA-CLEAR NT®) is added to the vessel, along with a small drop of acetone. The vessel is heated and allowed to cool. The reaction undergoes a series of color changes over time. A precipitate collects at the bottom of the vessel. The reaction product is referred to in this specification as 1346. This synthesis demonstrated the reaction's sensitivity to the presence of acetone, which facilitates the lactone modification.

EXAMPLE 14 High Oleic Canola Oil with Ketone Modification

27.0 g. Mn(OAc)₂.4H₂O. and 140 g. of acetic acid are mixed in a reaction vessel. 4.1 g. of KMnO₄ is added. 47.6 g. acetic anhydride is added. 8.8 g. of a refined, bleached and deodorized high oleic canola oil and 200 ml of acetone are added to the vessel, which is heated and allowed to cool. The reaction undergoes a series of color changes over time. A precipitate collects at the bottom of the vessel. The reaction product is referred to in this specification as 1347.

EXAMPLE 15 Soybean Oil with Lactone Modification

27.0 g. Mn(OAc)₂.4H₂O. and 139.5 g. of acetic acid are mixed in a reaction vessel. 4.1 g. of KMnO₄ is added. 47.7 g. acetic anhydride is added. 25.4 g. of a soybean oil is added to the vessel, which is heated and allowed to cool. The reaction undergoes a series of color changes over time. A precipitate collects at the bottom of the vessel. The reaction product is referred to in this specification as 1977.

EXAMPLE 16 Soybean Oil with Ketone Modification

27.0 g. Mn(OAc)₂.4H₂O. and 139.5 g. of acetic acid are mixed in a reaction vessel. 4.1 g. of KMnO₄ is added. 47.8 g. acetic anhydride is added. 25.4 g. of a soybean oil and 200 ml of acetone are added to the vessel, which is heated and allowed to cool. The reaction undergoes a series of color changes over time. A precipitate collects at the bottom of the vessel. The reaction product is referred to in this specification as 1976.

EXAMPLE 17 TFMO Characterization of Modified Soybean Oils

The following samples were characterized using the TFMO methodology

described above: 1756, 1757, 1976, 1977, 0458 and 0459. The samples were heated at 150° C. for 60 minutes and/or 120 minutes. The results are presented in Table 3 below:

TABLE 3 TFMO Characterization of Modified Soybean Oils at 150 C. % Volatiles % Volatiles (120 % Deposits % Deposits SAMPLE (60 minutes) minutes) (60 minutes) (120 minutes) 1757 4 7 8 34 1756 4 6 20 43 1976 3 25 1977 3 19 0458 1 1 0459 0 1 Untreated oil 2 17

Samples 0458 and 0459 were also characterized using TFMO at 200° C. for 120 minutes. The results are presented in Table 4:

TABLE 4 TFMO Characterization of Modified Soybean Oils at 200 C. % Volatiles % Deposits SAMPLE (120 minutes) (120 minutes) 0458 5 8 0459 5 21

This example demonstrates that increasing the reactant concentrations, as in samples 0458 and 0459, results in reaction products having an increased oxidative stability as compared to untreated oil and as compared to the reaction products of the lower concentration reactions.

EXAMPLE 18 TFMO Characterization of Modified Partially Hydrogenated Soybean Oils

Samples 1085 and 1086 were characterized using the TFMO methodology described above by heating at 200° C. for 60 minutes and 120 minutes. The results are presented in Table 5 below:

TABLE 5 TFMO Characterization of Modified Partially Hydrogenated Soybean Oils at 200 C. % Volatiles % Volatiles % Deposits % Deposits SAMPLE (60 minutes) (120 minutes) (60 minutes) (120 minutes) 1085 10 12 9 8 1086 8 11 7 17

Both samples appear to be oxidatively stable.

EXAMPLE 19 TFMO Characterization of Modified High Oleic Canola Oils

Samples 1346 and 1347 were characterized using the TFMO methodology described above by heating at 200° C. for 60 minutes and 120 minutes. The results are presented in Table 5 below:

TABLE 5 TFMO Characterization of Modified High Oleic Canola Oils at 200 C. % Volatiles % Volatiles (120 % Deposits % Deposits SAMPLE (60 minutes) minutes) (60 minutes) (120 minutes) 1346 11 11 34 58 1347 6 9 5 6 Untreated oil 11 10 30 59

Sample 1346 (lactone reaction product) appears to be as stable as the control oil. Sample 1347 (ketone reaction product) demonstrates an improved oxidative stability.

EXAMPLE 20 DSC Characterization of Modified Soybean Oils

DSC was performed on samples 1976 and 1977 to characterize the changes in crystallinity resulting from modification. The DSC protocol was as follows: 1) Hold samples for 5.0 minutes at 25.00° C.; 2) Cool samples from 25.00° C. to −70.00° C. at a cooling rate of 10.00° C. per minute; 3) Hold samples for 30.0 minutes at −70.00° C.; 4) Heat samples from −70.00° C. to 25.00° C. at a heating rate of 5.00° C. per minute. The resulting data is presented in Table 6:

TABLE 6 DSC Characterization of Modified Soybean Oils AREA UNDER DSC CURVE AREA UNDER DSC CURVE SAMPLE DURING COOLING (mJ) DURING HEATING (mJ) 1976 72.041 −54.558 1977 37.563 −70.257 Untreated oil 386.726 −115.271

The decrease in the area under the DSC curve for both treated samples demonstrates a decrease in crystallinity for the treated soybean oils. This decrease in crystallinity correlates with improved low temperature performance and a decreased pour point. Additionally, an increase in the viscosity of the treated oils as compared to the untreated oil, along with a decrease in the rate of solidification, was visually observed.

DSC was performed on samples 0823 and 0824 to characterize the changes in crystallinity resulting from modification. The DSC protocol was as follows: 1) Hold samples for 10.0 minutes at 80.00° C.; 2) Cool samples from 80.00° C. to −60.00° C. at a cooling rate of 10.00° C. per minute; 3) Hold samples for 30.0 minutes at −60.00° C.; 4) Heat samples from −60.00° C. to 80.0° C. at a heating rate of 5.00° C. per minute. The resulting data is presented in Table 7:

TABLE 7 DSC Characterization of Modified Partially Hydrogenated Soybean Oils AREA UNDER DSC CURVE AREA UNDER DSC CURVE SAMPLE DURING COOLING (MJ) DURING HEATING (MJ) 0823 640.573 −482.113 0824 179.290 −335.421 Untreated 674.484 −761.004 oil

The decrease in the area under the DSC curve for both treated samples demonstrates a decrease in crystallinity for the treated partially hydrogenated soybean oils, in particular the ketone modified partially hydrogenated soybean oil. Additionally, an increase in the viscosity of the treated oils as compared to the untreated oil, along with a decrease in the rate of solidification, was visually observed.

EXAMPLE 21 DSC Characterization of Modified High Oleic Canola Oils

DSC was performed on samples 0823 and 0824 to characterize the changes in crystallinity resulting from modification. The DSC protocol was as follows: 1) Hold samples for 10.0 minutes at 80.00° C.; 2) Cool samples from 80.00° C. to −60.00° C. at a cooling rate of 10.00° C. per minute; 3) Hold samples for 30.0 minutes at −60.00° C.; 4) Heat samples from −60.00° C. to 80.00° C. at a heating rate of 5.00° C. per minute. The resulting data is presented in Table 8:

TABLE 8 DSC Characterization of Modified High Oleic Canola Oils AREA UNDER DSC CURVE AREA UNDER DSC CURVE SAMPLE DURING COOLING (mJ) DURING HEATING (mJ) 1346 0 0 0824 16.930 0 Untreated 375.677 0 oil

The decrease in the area under the DSC curve for both treated samples demonstrates a decrease in crystallinity for the treated high oleic canola oils. Additionally, an increase in the viscosity of the treated oils as compared to the untreated oil, along with a decrease in the rate of solidification, was visually observed.

While the invention has been described with reference to certain embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims. 

1. A triglyceride having the structure:

in which R¹, R², and R³ are independently fatty acyl moieties, wherein at least one fatty acyl moiety of the triglyceride has a pendant ketone substitution.
 2. The triglyceride of claim 1 in which R¹, R², and R³ are independently palmitoleic acyl, stearic acyl, oleic acyl, linoleic acyl, or linolenic acyl.
 3. A lubricant formulation consisting essentially of the formulation of claim
 1. 4. A hydraulic fluid formulation consisting essentially of the formulation of claim
 1. 5. A dielectric fluid formulation consisting essentially of the formulation of claim
 1. 6. An intermediate for polymer synthesis consisting essentially of the hydrogenated formulation of claim
 1. 7. An intermediate for polymer synthesis consisting essentially of the hydroxylated formulation of claim
 1. 8. A method for modifying ethylenic unsaturation in a triglyceride, comprising: providing a triglyceride having at least one fatty acyl moiety with a site of unsaturation, the triglyceride having the structure:

in which R¹, R², and R³ are independently fatty acyl moieties, with the restriction that at least one of R¹, R², and R³ is an ethylenically unsaturated fatty acyl moiety having at least one site of unsaturation available for lactone substitution; and reacting the triglyceride with a carboxylic acid having at least two carbon atoms, forming a lactone on said at least one site of unsaturation.
 9. The method of claim 8, in which at least one of R¹, R², and R³ is palmitoleic acyl, oleic acyl, linoleic acyl, linolenic acyl, alpha-eleostearic acyl, ricinoleic acyl, gadoleic acyl, arachidonic acyl, cetoleic acyl, or erucic acyl.
 10. The method of claim 8, in which R¹, R², and R³ are independently palmitoleic acyl, stearic acyl, oleic acyl, linoleic acyl, or linolenic acyl.
 11. The method of claim 8, in which the triglyceride comprises soybean oil triglyceride, partially hydrogenated soybean oil triglyceride, canola oil triglyceride, high oleic canola oil triglyceride, cottonseed oil triglyceride, rapeseed oil triglyceride, palm oil triglyceride, triglyceride of palm oil fractions, corn oil triglycerides, triglycerides made from distilled tall oil, partially hydrogenated forms of any of the above oil triglycerides, or a combination of two or more of these.
 12. The method of claim 8, in which the carboxylic acid comprises acetic acid, propanoic acid, butanoic acid, pentanoic acid, or hexanoic acid or a combination of two or more of these.
 13. The method of claim 8, in which the carboxylic acid comprises acetic acid.
 14. The method of claim 8, in which the reaction is carried out in the presence of a metal ion.
 15. The method of claim 8, in which the reaction is carried out in the presence of a metal ion comprising Mn, V, or Ce.
 16. The method of claim 8, in which the reaction is carried out in the presence of Mn³⁺.
 17. The method of claim 8, in which the reaction is carried out in the presence of manganese triacetate.
 18. The method of claim 8, in which the reaction is carried out in the presence of an electron acceptor.
 19. A method for modifying ethylenic unsaturation in a triglyceride, comprising: providing a triglyceride having at least one fatty acyl moiety with a site of unsaturation, the triglyceride having the structure:

in which R¹, R², and R³ are independently fatty acyl moieties, with the restriction that at least one of R¹, R², and R³ is an ethylenically unsaturated fatty acyl moiety having at least one site of unsaturation available for ketone substitution; and reacting the triglyceride with a ketone, forming a ketone on said at least one site of unsaturation.
 20. The method of claim 19, in which at least one of R¹, R², and R³ is palmitoleic acyl, oleic acyl, linoleic acyl, linolenic acyl, alpha-eleostearic acyl, ricinoleic acyl, gadoleic acyl, arachidonic acyl, cetoleic acyl, or erucic acyl.
 21. The method of claim 19, in which R¹, R², and R³ are independently palmitoleic acyl, stearic acyl, oleic acyl, linoleic acyl, or linolenic acyl.
 22. The method of claim 19, in which the triglyceride comprises soybean oil triglyceride, canola oil triglyceride, high oleic canola oil triglyceride, cottonseed oil triglyceride, rapeseed oil triglyceride, palm oil triglyceride, triglyceride of palm oil fractions, corn oil triglycerides, triglycerides made from distilled tall oil, partially hydrogenated forms of any of the above oil triglycerides, or a combination of two or more of these.
 23. The method of any of claim 19, in which the ketone comprises acetone, pentane-2,4-dione, benzophenone, cyclohexanone, diacetone alcohol, diisobutyl ketone, isophorone, methyl amyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isobutyl ketone, or a combination of two or more of these.
 24. The method of claim 19, in which the ketone comprises acetone.
 25. The method of claim 19, in which the reaction is carried out in the presence of a metal ion.
 26. The method of claim 19, in which the reaction is carried out in the presence of a metal ion comprising Mn, V, or Ce.
 27. The method of claim 19, in which the reaction is carried out in the presence of Mn³⁺.
 28. The method of claim 19, in which the reaction is carried out in the presence of manganese triacetate.
 29. The method of claim 19, in which the reaction is carried out in the presence of an electron acceptor.
 30. The method of claim 19, in which a carboxylate moiety is formed on at least one site of unsaturation.
 31. The triglyceride of claim 1, made by substituting a pendant ketone group for a site of ethylenic unsaturation in a fatty acyl of the triglyceride. 